Abstract

1,3,5,7-Tetrakis(tetrazol-5-yl)-adamantane (H4L) was probed as a building block for the synthesis of tetrazolato/halido coordination polymers with open-network structures. MCl2 (M = Cu, Cd, Zn, Mn) was reacted with H4L in DMF at 70 degrees C to yield Cu4Cl4L(DMF)(5)]center dot DMF, 1; Cd4Cl4L(DMF)(7)]center dot DMF, 2; Zn3Cl2L(DMF)(4)]center dot 2DMF, 3 and Mn2L(DMF)(2)(MeOH)(4)]center dot DMF center dot 2MeOH center dot 2H(2)O, 4.1 and 2 (Fddd) are nearly isostructural and have zeolitic structures with a {4(3).6(2).8}, gis or gismondine underlying net, where the rote of the tetrahedral nodes is served by the coordination bonded clusters and the adamantane moiety. 3 (P2(1)/n) has a porous structure composed of coordination bonded layers with a (4.8(2)) fes topology joined via trans-{Zn(tetrazolate)(2)(DMF)(4)) pillars with an overall topology of {4.6(2)}{4.6(6).8(3)}, fsc-3,5-Cmce-2. 4 (Pca2(1)) is composed of stacked (Mn2L) hexagonal networks. In 1 and 2 the ligand fulfills a symmetric role of a tetrahedral building block, while in 3 and 4 it fulfills rather a role of an effective trigonal unit. Methanol-exchanged and activated 1 displayed an unusual type IV isotherm with H2 type hysteresis for N-2 sorption with an expected uptake at high P/P-0, but with a smaller S-BET = 505.5 m(2) g(-1) compared to the calculated 1789 m(2) g(-1), which is a possible result of the framework's flexibility. For H-2 sorption 0.79 wt% (1 bar, 77 K) and 0.06 wt% (1 bar, RT) uptake and Q(st) = -7.2 kJ mol(-1) heat of adsorption (77 K) were recorded. Weak antiferromagnetic interactions were found in 1 and 4 with J(1) = -9.60(1), J(2) = -17.2(2), J(3) = -2.28(10) cm(-1) and J = -0.76 cm(-1) respectively. The formation of zeolitic structures in 1 and 2, the concept of structural `imprinting' of rigid building blocks, and design opportunities suggested 4 as a potential hexafunctionalized biadamantane building block.